Comprehensive Study of Zr-Doped Ni-Rich Cathode Materials Upon Lithiation and Co-Precipitation Synthesis Steps.

Ni-rich layered oxides LiNi1-x-yMnxCoyO2 (NMC811, x = 0.1 and y = 0.1) are considered promising cathode materials in lithium-ion batteries (LiBs) due to their high energy density. However, those suffer a severe capacity loss upon cycling at high delithiated states. The loss of performance over time can be retarded by Zr doping. Herein, a small amount of Zr is added to NMC811 material via two alternative pathways: during the formation of the transition metal (TM) hydroxide precursor at the co-precipitation step (0.1%-Zr-cp) and during the lithiation at the solid-state synthesis step (0.1%-Zr-ss). In this work, the crystallographic Zr uptake in both 0.1%-Zr-ss and 0.1%-Zr-cp is determined and quantified through synchrotron X-ray diffraction and X-ray absorption spectroscopy. We prove that the inclusion of Zr in the TM site for 0.1%-Zr-cp leads to an improvement of both specific capacity (156 vs 149 mAh/g) and capacity retention (85 vs 82%) upon 100 cycles compared to 0.1%-Zr-ss where the Zr does not diffuse into the active material and forms only an extra phase separated from the NMC811 particles.

High-Voltage Spinel Cathode Materials: Navigating the Structural Evolution for Lithium-Ion Batteries.

High-voltage LiNi0.5Mn1.5O4 (LNMO) spinel oxides are highly promising cobalt-free cathode materials to cater to the surging demand for lithium-ion batteries (LIBs). However, commercial application of LNMOs is still challenging despite decades of research. To address the challenge, the understanding of their crystallography and structural evolutions during synthesis and electrochemical operation is critical. This review aims to illustrate and to update the fundamentals of crystallography, phase transition mechanisms, and electrochemical behaviors of LNMOs. First, the research history of LNMO and its development into a LIB cathode material is outlined. Then the structural basics of LNMOs including the classic and updated views of the crystal polymorphism, interconversion between the polymorphs, and structure-composition relationship is reviewed. Afterward, the phase transition mechanisms of LNMOs that connect structural and electrochemical properties are comprehensively discussed from fundamental thermodynamics to operando dynamics at intra- and inter-particle levels. In addition, phase evolutions during overlithiation as well as thermal-/electrochemical-driven phase transformations of LNMOs are also discussed. Finally, recommendations are offered for the further development of LNMOs as well as other complex materials to unlock their full potential for future sustainable and powerful batteries.

Monitoring the Morphological Changes of Skeleton-PtCo Electrocatalyst during PEMFC Start-Up/Shut-Downprobed by in†situ WAXS and SAXS.

Advanced in situ analyses are indispensable for comprehending the catalyst aging mechanisms of Pt-based PEM fuel cell cathode materials, particularly during accelerated stress tests (ASTs). In this study, a combination of in situ small-angle and wide-angle X-ray scattering (SAXS & WAXS) techniques were employed to establish correlations between structural parameters (crystal phase, quantity, and size) of a highly active skeleton-PtCo (sk-PtCo) catalyst and their degradation cycles within the potential range of the start-up/shut-down (SUSD) conditions. Despite the complex case of the sk-PtCo catalyst comprising two distinct fcc alloy phases, our complementary techniques enabled in situ monitoring of structural changes in each crystal phase in detail. Remarkably, the in situ WAXS measurements uncover two primary catalyst aging processes, namely the cobalt depletion (regime I) followed by the crystallite growth via Ostwald ripening and/or particle coalescence (regime II). Additionally, in situ SAXS data reveal a continuous size growth over the AST. The Pt-enriched shell thickening based on the Co depletion within the first 100 SUSD cycles and particle growth induced by additional potential cycles were also collaborated by ex situ STEM-EELS. Overall, our work shows a comprehensive aging model for the sk-PtCo catalyst probed by complementary in situ WAXS and SAXS techniques.

In Situ and Operando X-ray Scattering Methods in Electrochemistry and Electrocatalysis.

Electrochemical and electrocatalytic processes are of key importance for the transition to a sustainable energy supply as well as for a wide variety of other technologically relevant fields. Further development of these processes requires in-depth understanding of the atomic, nano, and micro scale structure of the materials and interfaces in electrochemical devices under reaction conditions. We here provide a comprehensive review of in situ and operando studies by X-ray scattering methods, which are powerful and highly versatile tools to provide such understanding. We discuss the application of X-ray scattering to a wide variety of electrochemical systems, ranging from metal and oxide single crystals to nanoparticles and even full devices. We show how structural data on bulk phases, electrode-electrolyte interfaces, and nanoscale morphology can be obtained and describe recent developments that provide highly local information and insight into the composition and electronic structure. These X-ray scattering studies yield insights into the structure in the double layer potential range as well as into the structural evolution during electrocatalytic processes and phase formation reactions, such as nucleation and growth during electrodeposition and dissolution, the formation of passive films, corrosion processes, and the electrochemical intercalation into battery materials.

Imaging Voids and Defects Inside Li-Ion Cathode LiNi0.6Mn0.2Co0.2O2 Single Crystals.

Li-ion battery cathode active materials obtained from different sources or preparation methods often exhibit broadly divergent performance and stability despite no obvious differences in morphology, purity, and crystallinity. We show how state-of-the-art, commercial, nominally single crystalline LiNi0.6Mn0.2Co0.2O2 (NMC-622) particles possess extensive internal nanostructure even in the pristine state. Scanning X-ray diffraction microscopy reveals the presence of interlayer strain gradients, and crystal bending is attributed to oxygen vacancies. Phase contrast X-ray nano-tomography reveals two different kinds of particles, welded/aggregated, and single crystal like, and emphasizes the intra- and interparticle heterogeneities from the nano- to the microscale. It also detects within the imaging resolution (100 nm) substantial quantities of nanovoids hidden inside the bulk of two-thirds of the overall studied particles (around 3000), with an average value of 12.5%v per particle and a mean size of 148 nm. The powerful combination of both techniques helps prescreening and quantifying the defective nature of cathode material and thus anticipating their performance in electrode assembly/battery testing.

Interfacial alloying between lead halide perovskite crystals and hybrid glasses.

The stellar optoelectronic properties of metal halide perovskites provide enormous promise for next-generation optical devices with excellent conversion efficiencies and lower manufacturing costs. However, there is a long-standing ambiguity as to whether the perovskite surface/interface (e.g. structure, charge transfer or source of off-target recombination) or bulk properties are the more determining factor in device performance. Here we fabricate an array of CsPbI3 crystal and hybrid glass composites by sintering and globally visualise the property-performance landscape. Our findings reveal that the interface is the primary determinant of the crystal phases, optoelectronic quality, and stability of CsPbI3. In particular, the presence of a diffusion "alloying" layer is discovered to be critical for passivating surface traps, and beneficially altering the energy landscape of crystal phases. However, high-temperature sintering results in the promotion of a non-stoichiometric perovskite and excess traps at the interface, despite the short-range structure of halide is retained within the alloying layer. By shedding light on functional hetero-interfaces, our research offers the key factors for engineering high-performance perovskite devices.

Defects and nanostrain gradients control phase transition mechanisms in single crystal high-voltage lithium spinel.

Lithiation dynamics and phase transition mechanisms in most battery cathode materials remain poorly understood, because of the challenge in differentiating inter- and intra-particle heterogeneity. In this work, the structural evolution inside Li1-xMn1.5Ni0.5O4 single crystals during electrochemical delithiation is directly resolved with operando X-ray nanodiffraction microscopy. Metastable domains of solid-solution intermediates do not appear associated with the reaction front between the lithiated and delithiated phases, as predicted by current phase transition theory. Instead, unusually persistent strain gradients inside the single crystals suggest that the shape and size of solid solution domains are instead templated by lattice defects, which guide the entire delithiation process. Morphology, strain distributions, and tilt boundaries reveal that the (Ni2+/Ni3+) and (Ni3+/Ni4+) phase transitions proceed through different mechanisms, offering solutions for reducing structural degradation in high voltage spinel active materials towards commercially useful durability. Dynamic lattice domain reorientation during cycling are found to be the cause for formation of permanent tilt boundaries with their angular deviation increasing during continuous cycling.

Anodic and Cathodic Platinum Dissolution Processes Involve Different Oxide Species.

The degradation of Pt-containing oxygen reduction catalysts for fuel cell applications is strongly linked to the electrochemical surface oxidation and reduction of Pt. Here, we study the surface restructuring and Pt dissolution mechanisms during oxidation/reduction for the case of Pt(100) in 0.1 M HClO4 by combining operando high-energy surface X-ray diffraction, online mass spectrometry, and density functional theory. Our atomic-scale structural studies reveal that anodic dissolution, detected during oxidation, and cathodic dissolution, observed during the subsequent reduction, are linked to two different oxide phases. Anodic dissolution occurs predominantly during nucleation and growth of the first, stripe-like oxide. Cathodic dissolution is linked to a second, amorphous Pt oxide phase that resembles bulk PtO2 and starts to grow when the coverage of the stripe-like oxide saturates. In addition, we find the amount of surface restructuring after an oxidation/reduction cycle to be potential-independent after the stripe-like oxide has reached its saturation coverage.

Imaging the strain evolution of a platinum nanoparticle under electrochemical control.

Surface strain is widely employed in gas phase catalysis and electrocatalysis to control the binding energies of adsorbates on active sites. However, in situ or operando strain measurements are experimentally challenging, especially on nanomaterials. Here we exploit coherent diffraction at the new fourth-generation Extremely Brilliant Source of the European Synchrotron Radiation Facility to map and quantify strain within individual Pt catalyst nanoparticles under electrochemical control. Three-dimensional nanoresolution strain microscopy, together with density functional theory and atomistic simulations, show evidence of heterogeneous and potential-dependent strain distribution between highly coordinated ({100} and {111} facets) and undercoordinated atoms (edges and corners), as well as evidence of strain propagation from the surface to the bulk of the nanoparticle. These dynamic structural relationships directly inform the design of strain-engineered nanocatalysts for energy storage and conversion applications.

Selenium Nanowire Formation by Reacting Selenate with Magnetite.

The mobility of 79Se, a fission product of 235U and long-lived radioisotope, is an important parameter in the safety assessment of radioactive nuclear waste disposal systems. Nonradioactive selenium is also an important contaminant of drainage waters from black shale mountains and coal mines. Highly mobile and soluble in its high oxidation states, selenate (Se(VI)O42-) and selenite (Se(IV)O32-) oxyanions can interact with magnetite, a mineral present in anoxic natural environments and in steel corrosion products, thereby being reduced and consequently immobilized by forming low-solubility solids. Here, we investigated the sorption and reduction capacity of synthetic nanomagnetite toward Se(VI) at neutral and acidic pH, under reducing, oxygen-free conditions. The additional presence of Fe(II)aq, released during magnetite dissolution at pH 5, has an effect on the reduction kinetics. X-ray absorption spectroscopy analyses revealed that, at pH 5, trigonal gray Se(0) formed and that sorbed Se(IV) complexes remained on the nanoparticle surface during longer reaction times. The Se(0) nanowires grew during the reaction, which points to a complex transport mechanism of reduced species or to active reduction sites at the tip of the Se(0) nanowires. The concomitant uptake of aqueous Fe(II) and Se(VI) ions is interpreted as a consequence of small pH oscillations that result from the Se(VI) reduction, leading to a re-adsorption of aqueous Fe(II) onto the magnetite, renewing its reducing capacity. This effect is not observed at pH 7, where we observed only the formation of Se(0) with slow kinetics due to the formation of an oxidized maghemite layer. This indicates that the presence of aqueous Fe(II) may be an important factor to be considered when examining the environmental reactivity of magnetite.

Impact of Carbon N-Doping and Pyridinic-N Content on the Fuel Cell Performance and Durability of Carbon-Supported Pt Nanoparticle Catalysts.

Cathode catalyst layers of proton exchange membrane fuel cells (PEMFCs) typically consist of carbon-supported platinum catalysts with varying weight ratios of proton-conducting ionomers. N-Doping of carbon support materials is proposed to enhance the performance and durability of the cathode layer under operating conditions in a PEMFC. However, a detailed understanding of the contributing N-moieties is missing. Here, we report the successful synthesis and fuel cell implementation of Pt electrocatalysts supported on N-doped carbons, with a focus on the analysis of the N-induced effect on catalyst performance and durability. A customized fluidized bed reduction reactor was used to synthesize highly monodisperse Pt nanoparticles deposited on N-doped carbons (N-C), the catalytic oxygen reduction reaction activity and stability of which matched those of state-of-the-art PEMFC catalysts. Operando high-energy X-ray diffraction experiments were conducted using a fourth generation storage ring; the light of extreme brilliance and coherence allows investigating the impact of N-doping on the degradation behavior of the Pt/N-C catalysts. Tests in liquid electrolytes were compared with tests in membrane electrode assemblies in single-cell PEMFCs. Our analysis refines earlier views on the subject of N-doped carbon catalyst supports: it provides evidence that heteroatom doping and thus the incorporation of defects into the carbon backbone do not mitigate the carbon corrosion during high-potential cycling (1-1.5 V) and, however, can promote the cell performance under usual PEMFC operating conditions (0.6-0.9 V).

Electrochemical Strain Dynamics in Noble Metal Nanocatalysts.

The theoretical design of effective metal electrocatalysts for energy conversion and storage devices relies greatly on supposed unilateral effects of catalysts structure on electrocatalyzed reactions. Here, by using high-energy X-ray diffraction from the new Extremely Brilliant Source of the European Synchrotron Radiation Facility (ESRF-EBS) on device-relevant Pd and Pt nanocatalysts during cyclic voltammetry experiments in liquid electrolytes, we reveal the near ubiquitous feedback from various electrochemical processes on nanocatalyst strain. Beyond challenging and extending the current understanding of practical nanocatalysts behavior in electrochemical environment, the reported electrochemical strain provides experimental access to nanocatalysts absorption and adsorption trends (i.e., reactivity and stability descriptors) operando. The ease and power in monitoring such key catalyst properties at new and future beamlines is foreseen to provide a discovery platform toward the study of nanocatalysts encompassing a large variety of applications, from model environments to the device level.

Liquid-phase sintering of lead halide perovskites and metal-organic framework glasses.

Lead halide perovskite (LHP) semiconductors show exceptional optoelectronic properties. Barriers for their applications, however, lie in their polymorphism, instability to polar solvents, phase segregation, and susceptibility to the leaching of lead ions. We report a family of scalable composites fabricated through liquid-phase sintering of LHPs and metal-organic framework glasses. The glass acts as a matrix for LHPs, effectively stabilizing nonequilibrium perovskite phases through interfacial interactions. These interactions also passivate LHP surface defects and impart bright, narrow-band photoluminescence with a wide gamut for creating white light-emitting diodes (LEDs). The processable composites show high stability against immersion in water and organic solvents as well as exposure to heat, light, air, and ambient humidity. These properties, together with their lead self-sequestration capability, can enable breakthrough applications for LHPs.

Morphology and mechanism of highly selective Cu(II) oxide nanosheet catalysts for carbon dioxide electroreduction.

Cu oxides catalyze the electrochemical carbon dioxide reduction reaction (CO2RR) to hydrocarbons and oxygenates with favorable selectivity. Among them, the shape-controlled Cu oxide cubes have been most widely studied. In contrast, we report on novel 2-dimensional (2D) Cu(II) oxide nanosheet (CuO NS) catalysts with high C2+ products, selectivities (> 400 mA cm-2) in gas diffusion electrodes (GDE) at industrially relevant currents and neutral pH. Under applied bias, the (001)-orientated CuO NS slowly evolve into highly branched, metallic Cu0 dendrites that appear as a general dominant morphology under electrolyte flow conditions, as attested by operando X-ray absorption spectroscopy and in situ electrochemical transmission electron microscopy (TEM). Millisecond-resolved differential electrochemical mass spectrometry (DEMS) track a previously unavailable set of product onset potentials. While the close mechanistic relation between CO and C2H4 was thereby confirmed, the DEMS data help uncover an unexpected mechanistic link between CH4 and ethanol. We demonstrate evidence that adsorbed methyl species, *CH3, serve as common intermediates of both CH3H and CH3CH2OH and possibly of other CH3-R products via a previously overlooked pathway at (110) steps adjacent to (100) terraces at larger overpotentials. Our mechanistic conclusions challenge and refine our current mechanistic understanding of the CO2 electrolysis on Cu catalysts.

Thermal Stability of Thiolated DNA SAMs in Buffer: Revealing the Influence of Surface Crystallography and DNA Coverage via In Situ Combinatorial Surface Analysis.

The thermal stability of thiol based DNA SAMs prepared on gold surfaces is an important parameter that is correlated to sensor lifetime. The thermal stability of DNA SAMs was evaluated in aqueous buffer through the use of fluorophore labeled DNA, a single crystal gold bead electrode, and microscopy. The stability of different crystallographic regions on the electrode was studied for thermal treatments up to 95 °C for 90 min. Using a in situ combinatorial surface analytical measurement showed that the crystallography of the underlying gold surface played a significant role, with the square or rectangular lattices (e.g., 110, 100, 210) having the highest stability. Surfaces with hexagonal lattices (e.g., 111, 311, 211) were less stable toward thermal treatments. These crystallographic trends were observed for both high and low coverage DNA SAMs. High coverage DNA SAMs were the most stable, with stability decreasing with decreasing coverage on average. Increasing DNA SAM coverage appears to slow the kinetics of thermal desorption, but the coordination to the underlying surface determined their relative stability. Preparing the DNA SAMs under nominally similar conditions were found to create surfaces that were similar at room temperature, but had significantly different thermal stability. Optimal DNA sensing with these surfaces most often requires low coverage DNA SAMs which results in poor thermal stability, which is predictive of a poor shelf life, making optimization of both parameters challenging. Furthermore, the crystallographically specific results should be taken into account when studying the typically used polycrystalline substrates since the underlying surface crystallography maybe different for different samples. It appears that preparing DNA SAMs with low coverage and significant thermal stability will be challenging using the current SAM preparation procedures.

Measuring and Controlling the Local Environment of Surface-Bound DNA in Self-Assembled Monolayers on Gold When Prepared Using Potential-Assisted Deposition.

DNA self-assembled monolayers (SAMs) were prepared using potential-assisted deposition on clean gold single-crystal bead electrodes under a number of conditions (constant or square-wave potential perturbations in TRIS or phosphate immobilization buffers with and without Cl-). The local environment around the fluorophore-labeled DNA tethered to the electrode surface was characterized using in situ fluorescence microscopy during electrochemical measurements as a function of the underlying surface crystallography. Potential-assisted deposition from a TRIS buffer containing Cl- created DNA SAMs that were uniformly distributed on the surface with little preference to the underlying crystallography. A constant (+0.4 V/SCE) or a square-wave potential perturbation (+0.4 to -0.3 V/SCE, 50 Hz) resulted in similar DNA-modified surfaces in TRIS immobilization buffer. Deposition using a square-wave potential without Cl- resulted in lower DNA surface coverage. Despite this, the local environment around the DNA in the SAM appears to be densely packed. This implies the formation of clusters of densely packed DNA in the SAM. This effect was also demonstrated when depositing from a phosphate buffer. DNA clusters were significantly reduced when Cl- was present in the buffer. Clusters were most prevalent on the low-index plane surfaces (e.g., {111} and {100}) and less on the higher-index planes (e.g., {210} or {311}). A mechanism is proposed to rationalize the formation of DNA-clustered regions for deposition using a square-wave potential perturbation. The conditions for creating clusters of DNA in a SAM or for preventing these clusters from forming provide an approach for tailoring the surfaces used for biosensing.

Direct Mapping of Heterogeneous Surface Coverage in DNA-Functionalized Gold Surfaces with Correlated Electron and Fluorescence Microscopy.

The characterization of biofunctionalized surfaces such as alkanethiol self-assembled monolayers (SAMs) on gold modified with DNA or other biomolecules is a challenging analytical problem, and access to a routine method is desirable. Despite substantial investigation from structural and mechanistic perspectives, robust and high-throughput metrology tools for SAMs remain elusive but essential for the continued development of these devices. We demonstrate that scanning electron microscopy (SEM) can provide image contrast of the molecular interface during SAM functionalization. The high-speed, large magnification range, and ease of use make this widely available technique a powerful platform for measuring the structure and composition of SAM surfaces. This increased throughput allows for a better understanding of the nonideal spatial heterogeneity characteristic of SAMs utilized in real-world conditions. SEM image contrast is characterized through the use of fluorescently labeled DNA, which enables correlative SEM and fluorescence microscopy. This allows identification of the DNA-modified regions at resolutions that approach the size of the biomolecule. The effect of electron beam irradiation dose is explored, which leads to straightforward lithographic patterning of DNA SAMs with nanometer resolution and with control over the surface coverage of specifically adsorbed DNA.

Phosphonate monoesters as carboxylate-like linkers for metal organic frameworks.

Bidentate phosphonate monoesters are analogues of popular dicarboxylate linkers in MOFs, but with an alkoxy tether close to the coordinating site. Herein, we report 3-D MOF materials based upon phosphonate monoester linkers. Cu(1,4-benzenediphosphonate bis(monoalkyl ester), CuBDPR, with an ethyl tether is nonporous; however, the methyl tether generates an isomorphous framework that is porous and captures CO(2) with a high isosteric heat of adsorption of 45 kJ mol(-1). Computational modeling reveals that the CO(2) uptake is extremely sensitive both to the flexing of the structure and to the orientation of the alkyl tether.